CN104710386B - A kind of 2,1,3 diazosulfide derivatives and its preparation method and application - Google Patents
A kind of 2,1,3 diazosulfide derivatives and its preparation method and application Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- OBISXEJSEGNNKL-UHFFFAOYSA-N dinitrogen-n-sulfide Chemical class [N-]=[N+]=S OBISXEJSEGNNKL-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 125000001424 substituent group Chemical group 0.000 claims abstract description 70
- 239000000463 material Substances 0.000 claims abstract description 64
- 230000002950 deficient Effects 0.000 claims abstract description 52
- 239000000126 substance Substances 0.000 claims abstract description 44
- 238000000034 method Methods 0.000 claims abstract description 21
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 16
- 239000011259 mixed solution Substances 0.000 claims description 41
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 22
- 125000000217 alkyl group Chemical group 0.000 claims description 22
- 229910052799 carbon Inorganic materials 0.000 claims description 22
- 230000004048 modification Effects 0.000 claims description 17
- 238000012986 modification Methods 0.000 claims description 17
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 15
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 15
- 239000003054 catalyst Substances 0.000 claims description 13
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 12
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- NNJVILVZKWQKPM-UHFFFAOYSA-N Lidocaine Chemical compound CCN(CC)CC(=O)NC1=C(C)C=CC=C1C NNJVILVZKWQKPM-UHFFFAOYSA-N 0.000 claims description 11
- 229960004194 lidocaine Drugs 0.000 claims description 11
- 239000000758 substrate Substances 0.000 claims description 11
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 150000003053 piperidines Chemical class 0.000 claims description 9
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- FCEHBMOGCRZNNI-UHFFFAOYSA-N thianaphthalene Natural products C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 claims description 7
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- 150000004866 oxadiazoles Chemical class 0.000 claims 1
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- 238000004528 spin coating Methods 0.000 description 33
- 239000011521 glass Substances 0.000 description 23
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical group CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 20
- 229920000301 poly(3-hexylthiophene-2,5-diyl) polymer Polymers 0.000 description 15
- 239000000047 product Substances 0.000 description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 14
- -1 amino, dimethylamino Chemical group 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- 239000011368 organic material Substances 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 239000004332 silver Substances 0.000 description 4
- 0 CC(*)(C1)CC(C)=CC1C(C#N)C#N Chemical compound CC(*)(C1)CC(C)=CC1C(C#N)C#N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 150000002220 fluorenes Chemical class 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 150000004867 thiadiazoles Chemical class 0.000 description 3
- 229930192474 thiophene Natural products 0.000 description 3
- PYOLJOJPIPCRDP-UHFFFAOYSA-N 1,1,3-trimethylcyclohexane Chemical compound CC1CCCC(C)(C)C1 PYOLJOJPIPCRDP-UHFFFAOYSA-N 0.000 description 2
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 description 2
- 229920003026 Acene Polymers 0.000 description 2
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 206010011224 Cough Diseases 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- 229940049706 benzodiazepine Drugs 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
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- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- HKNRNTYTYUWGLN-UHFFFAOYSA-N dithieno[3,2-a:2',3'-d]thiophene Chemical compound C1=CSC2=C1SC1=C2C=CS1 HKNRNTYTYUWGLN-UHFFFAOYSA-N 0.000 description 2
- 229910003472 fullerene Inorganic materials 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- MRNHPUHPBOKKQT-UHFFFAOYSA-N indium;tin;hydrate Chemical group O.[In].[Sn] MRNHPUHPBOKKQT-UHFFFAOYSA-N 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 2
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
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- VJYJJHQEVLEOFL-UHFFFAOYSA-N thieno[3,2-b]thiophene Chemical compound S1C=CC2=C1C=CS2 VJYJJHQEVLEOFL-UHFFFAOYSA-N 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- DTGKSKDOIYIVQL-NQMVMOMDSA-N (+)-Borneol Natural products C1C[C@]2(C)[C@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-NQMVMOMDSA-N 0.000 description 1
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical compound C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 1
- QTUUBOZSGQFLRZ-UHFFFAOYSA-N CC(C)(CC(C)=C1)CC1=C(C#N)C#N Chemical compound CC(C)(CC(C)=C1)CC1=C(C#N)C#N QTUUBOZSGQFLRZ-UHFFFAOYSA-N 0.000 description 1
- ZEPJMSAVYHTSGB-UHFFFAOYSA-N CC(C)(CC(CCc(c1n[s]nc11)ccc1N(C)C)=C1)CC1=C(C#N)C#N Chemical compound CC(C)(CC(CCc(c1n[s]nc11)ccc1N(C)C)=C1)CC1=C(C#N)C#N ZEPJMSAVYHTSGB-UHFFFAOYSA-N 0.000 description 1
- XYBUCJYJVULPHW-UHFFFAOYSA-N CC(OC(C)=C1)=CC1=C(C#N)C#N Chemical compound CC(OC(C)=C1)=CC1=C(C#N)C#N XYBUCJYJVULPHW-UHFFFAOYSA-N 0.000 description 1
- QSNQUGHMBXUIFP-VQHVLOKHSA-N CC(OC(C=[IH])=C1)=C/C1=C(/C#N)\N Chemical compound CC(OC(C=[IH])=C1)=C/C1=C(/C#N)\N QSNQUGHMBXUIFP-VQHVLOKHSA-N 0.000 description 1
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- BXAGHEQXRGEOEO-UHFFFAOYSA-N CN(C)c1ccc(C(I)=O)c2n[s]nc12 Chemical compound CN(C)c1ccc(C(I)=O)c2n[s]nc12 BXAGHEQXRGEOEO-UHFFFAOYSA-N 0.000 description 1
- DCEPOZLIDUBGTK-UHFFFAOYSA-N CN(C)c1ccc(C=O)c2n[s]nc12 Chemical compound CN(C)c1ccc(C=O)c2n[s]nc12 DCEPOZLIDUBGTK-UHFFFAOYSA-N 0.000 description 1
- 240000005636 Dryobalanops aromatica Species 0.000 description 1
- ZCKSUPBXSGFPRV-UHFFFAOYSA-N O=Cc(c1n[s]nc11)ccc1I Chemical compound O=Cc(c1n[s]nc11)ccc1I ZCKSUPBXSGFPRV-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229960000846 camphor Drugs 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
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- 150000002148 esters Chemical class 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
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- 230000021715 photosynthesis, light harvesting Effects 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
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- 238000003756 stirring Methods 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D285/00—Heterocyclic compounds containing rings having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by groups C07D275/00 - C07D283/00
- C07D285/01—Five-membered rings
- C07D285/02—Thiadiazoles; Hydrogenated thiadiazoles
- C07D285/14—Thiadiazoles; Hydrogenated thiadiazoles condensed with carbocyclic rings or ring systems
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
- C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
- C07D417/06—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/80—Constructional details
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Photovoltaic Devices (AREA)
Abstract
The embodiments of the invention provide a kind of 2,1,3 diazosulfide derivatives；R in its chemical formula1For abundant electron substituents, R2And R3In one be electron deficient substituent and another be hydrogen atom, or R2And R3In two be electron deficient substituent.2,1, the 3 diazosulfide derivative electronic transmission performance is good, and material character is stable.Second aspect of the embodiment of the present invention provides a kind of preparation method of 2,1,3 diazosulfide derivative, and this method is simple, and obtained 2,1,3 diazosulfide derivative electronic transmission performance is good.The third aspect of the embodiment of the present invention provides a kind of embellishing cathode interface material, and the embellishing cathode interface material electronicses transmission performance is good and property is stable, and the energy conversion efficiency of organic solar batteries can be improved for organic solar batteries.Fourth aspect of the embodiment of the present invention provides a kind of organic solar batteries.
Description
Technical field
The present invention relates to organic material field, more particularly to a kind of 2,1,3- diazosulfide derivative and its preparation side
Method and application.
Background technology
Compared with traditional inorganic solar cell, organic solar batteries can be prepared on a flexible substrate, be had soft
The advantages of property, light, non-breakable and simple production process, increasingly it is valued by people.But organic solar batteries
Energy conversion efficiency is relatively low, and main cause is that the charge transport properties of the active layer material in organic solar batteries are poor, is made
Organic solar batteries absorb caused electronics and hole after luminous energy and can not form effective electric current, but it is compound after turn
The energy dissipations such as chemical conversion heat energy are fallen.In order that the better transmission of electronics and hole, increasing researcher start to be conceived to
The research of electrode interface decorative layer and electrode interface decorative material.
Embellishing cathode interface material need with charge transport properties it is good the advantages of, at present, embellishing cathode interface material
Predominantly polymeric material, such as poly- [9,9- dioctyl fluorenes -9,9- pair（N, N- DimethylAminopropyl）Fluorenes]（PFN）.But it polymerize
Thing material is not preferable embellishing cathode interface material enough, because polymeric material is not easily because extent of polymerization is in preparation process
There is inconsistent relative molecular weight together, this will cause its property unstability when in use.Therefore, seek a kind of electric charge to pass
The stable novel cathode modifying interface material of defeated functional and property seems extremely important.
The content of the invention
Derive to solve the above problems, first aspect of the embodiment of the present invention aims to provide a kind of 2,1,3- diazosulfide
Thing, the electronic transmission performance of 2,1, the 3- diazosulfide derivative is good and property is stable.Second aspect of the embodiment of the present invention
A kind of preparation method of 2,1,3- diazosulfide derivative is aimed to provide, this method is simple, obtained 2,1,3- benzo thiophene two
Zole derivatives electronic transmission performance is good and property is stable；The third aspect of the embodiment of the present invention aims to provide a kind of cathode interface and repaiied
Exterior material, the embellishing cathode interface material electronicses transmission performance is good and property is stable, can be with during for organic solar batteries
Improve the energy conversion efficiency of organic solar batteries；Fourth aspect of the embodiment of the present invention aims to provide a kind of organic solar electricity
Pond, organic solar batteries energy conversion efficiency height and stable performance.
In a first aspect, the embodiments of the invention provide a kind of 2,1,3- diazosulfide derivative, described 2,1,3- benzo
The chemical structural formula of thiadiazoles derivative such as formula（Ⅰ）It is shown：
Wherein, R1For abundant electron substituents, R2And R3In one be electron deficient substituent and another be hydrogen atom, or R2
And R3In two be electron deficient substituent.
Preferably, the R1For amino, dimethylamino or lignocaine.
Preferably, the R2And R3It independently is-CN ,-NO2、-COOR4、Or
Wherein, R4The alkyl for being 0~6 for carbon number.
Preferably, described 2, the chemical structural formula of 1,3- diazosulfide derivative is one kind in the d of I a of formula~formula I：
Wherein, R4The alkyl for being 0~6 for carbon number.
Described 2, contain abundant electron substituents and electron deficient substituent in 1,3- diazosulfide derivative, be unsymmetrical knot
Structure, electric dipole moment is produced in 2,1,3- diazosulfide derivative intramoleculars so that electronics has side in the transmission of the intramolecular
Tropism, improve electric transmission efficiency.2,1, the 3- diazosulfide derivative is during film forming is prepared, because it is from group
The characteristic of dress, electron deficient substituent is easily enriched in the photoelectric active layer position of battery, and abundant electron substituents are then easily enriched in the moon
Pole positions of materials.Electron deficient substituent be easy to from photoelectric active layer organic active layer material extract electronics, and by electronics with
The direction of electric dipole moment is transferred to abundant electron substituents position, is then extracted by cathode material, and the directionality for being advantageous to electronics passes
It is defeated, so as to improve the photoelectric transformation efficiency of battery.Meanwhile diazosulfide unit and electron deficient substituent form big conjugated body
System, has wider energy band and high electron affinity energy, improves 2, the electric transmission efficiency of 1,3- diazosulfide derivative.
Described 2,1,3- diazosulfide derivative is Small molecule organic materials, and molecular weight is fixed, and property is stable, overcomes
When embellishing cathode interface material is polymeric material in the prior art, material molecule amount is inconsistent to cause organic solar batteries steady
The problem of property difference, so as to improve the stability of organic solar batteries and energy conversion efficiency.
Second aspect, the embodiments of the invention provide a kind of preparation method of 2,1,3- diazosulfide derivative, including
Following steps：
Compound of the chemical structural formula as shown in formula A and the compound as shown in formula B are provided respectively,
A：B：
Wherein, R1For abundant electron substituents, R2And R3In one be electron deficient substituent and another be hydrogen atom, or R2
And R3In two be electron deficient substituent；
It is 1 by mol ratio under oxygen-free environment:1~1:10 compound as shown in formula A and the change as shown in formula B
Compound, which is added into the organic solvent containing catalyst, to be dissolved, and obtains mixed solution, by the mixed solution at 40 DEG C~150 DEG C
Lower carry out knoevenagel condensation, reaction time are 4~48 hours, obtain product, and the organic solvent is acetonitrile, second
Acid, toluene, acetic anhydride or N,N-dimethylformamide；Then stop reacting and be cooled to room temperature, by the product silicagel column
Chromatography method purifies, and obtains structural formula such as formula（Ⅰ）The shown 2,1,3- diazosulfide derivatives：
Preferably, the catalyst is piperidines, basic alumina or triethylamine.
Preferably, described 2, the chemical structural formula of 1,3- diazosulfide derivative is one kind in the d of I a of formula~formula I：
Wherein, R4The alkyl for being 0~6 for carbon number.
Second aspect of the embodiment of the present invention provides a kind of preparation method of 2,1,3- diazosulfide derivative, the preparation
Method is simple, and obtained 2,1,3- diazosulfide derivative electronic transmission performance is good and property is stable.
The third aspect, the embodiments of the invention provide a kind of embellishing cathode interface material, the embellishing cathode interface material
Chemical structural formula such as formula（Ⅰ）It is shown：
Wherein, R1For abundant electron substituents, R2And R3In one be electron deficient substituent and another be hydrogen atom, or R2
And R3In two be electron deficient substituent.
The inventive embodiments third aspect provides a kind of embellishing cathode interface material, and the embellishing cathode interface material electronicses pass
Defeated functional and property is stable, and the energy conversion effect of organic solar batteries can be improved during for organic solar batteries
Rate.
Fourth aspect, the embodiments of the invention provide a kind of organic solar batteries, the solar cell for it is formal too
It is positive can battery or trans solar cell, transparent substrates that the formal solar cell includes stacking gradually, anode layer, anode
Decorative layer, photoelectric active layer, embellishing cathode interface layer and cathode layer, the trans solar cell are transparent including stacking gradually
Substrate, cathode layer, embellishing cathode interface layer, photoelectric active layer, anode modification layer and anode layer, the embellishing cathode interface layer
The chemical structural formula of material such as formula（Ⅰ）It is shown：
Wherein, R1For abundant electron substituents, R2And R3In one be electron deficient substituent and another be hydrogen atom, or R2
And R3In two be electron deficient substituent.
Preferably, described 2, the chemical structural formula of 1,3- diazosulfide derivative is one kind in the d of I a of formula~formula I：
Wherein, R4The alkyl for being 0~6 for carbon number.
Fourth aspect of the embodiment of the present invention provides a kind of organic solar batteries, negative electrode circle of the organic solar batteries
The material of face decorative layer is the diazosulfide derivative of one kind 2,1,3- described in first aspect present invention, and the organic solar is electric
Pond energy conversion efficiency is high and property is stable.
First aspect of the embodiment of the present invention provides a kind of 2,1,3- diazosulfide derivative, 2,1, the 3- benzo thiophene two
Contain abundant electron substituents and electron deficient substituent in Zole derivatives simultaneously, be unsymmetric structure, cause 2,1,3- benzo thiophene two
Zole derivatives intramolecular produces electric dipole moment so that electronics has directionality in the transmission of the intramolecular, improves electric transmission
Efficiency.2,1, the 3- diazosulfide derivative is during film forming is prepared, due to the characteristic of its self assembly, electron deficient substitution
Base is easily enriched in the photoelectric active layer position of battery, and abundant electron substituents are then easily enriched in cathode material position.Electron deficient takes
Dai Ji is easy to extract electronics from the organic active layer material in photoelectric active layer, and electronics is transferred to the direction of electric dipole moment
Abundant electron substituents position, is then extracted by cathode material, is advantageous to the directional transmission of electronics, so as to improve the photoelectricity of battery
Conversion efficiency.Meanwhile diazosulfide unit and electron deficient substituent form big conjugated system, there is wider energy band and height
Electron affinity energy, improve the electric transmission efficiency of 2,1,3- diazosulfide derivative.The 2,1,3- diazosulfides
Derivative is Small molecule organic materials, and molecular weight is fixed, and property is stable, and overcoming embellishing cathode interface material in the prior art is
During polymeric material, material molecule amount inconsistent the problem of causing organic solar batteries stability difference, so as to improve it is organic too
The stability and energy conversion efficiency of positive energy battery.Second aspect of the embodiment of the present invention aims to provide a kind of 2,1,3- benzos thiophene two
The preparation method of Zole derivatives, the preparation method is simple, and obtained 2,1,3- diazosulfide derivative electronic transmission performance is good
Good and property is stable.The inventive embodiments third aspect aims to provide a kind of embellishing cathode interface material, the embellishing cathode interface material
Expect that electronic transmission performance is good and property is stable, the energy of organic solar batteries can be improved during for organic solar batteries
Conversion efficiency.Fourth aspect of the embodiment of the present invention aims to provide a kind of organic solar batteries, the moon of the organic solar batteries
The material of pole interface-modifying layer is 2,1,3- diazosulfide derivative described in first aspect present invention, and the organic solar is electric
Pond energy conversion efficiency height and stable performance.
Embodiment
As described below is the preferred embodiment of the embodiment of the present invention, it is noted that for the common skill of the art
For art personnel, on the premise of principle of the embodiment of the present invention is not departed from, some improvements and modifications can also be made, these improvement
The protection domain of the embodiment of the present invention is also considered as with retouching.
First aspect of the embodiment of the present invention provides a kind of 2,1,3- diazosulfide derivative, 2,1, the 3- benzo thiophene two
Contain abundant electron substituents and electron deficient substituent in Zole derivatives simultaneously, be advantageous to the directional transmission of electronics, so as to improve
The photoelectric transformation efficiency of battery, while the molecular weight of 2,1, the 3- diazosulfide derivative is single, property is stable.It is of the invention real
Apply a second aspect and aim to provide a kind of preparation method of 2,1,3- diazosulfide derivative, the preparation method is simple, is made
2,1,3- diazosulfide derivative electronic transmission performances are good and property is stable.The inventive embodiments third aspect aims to provide
A kind of embellishing cathode interface material, the embellishing cathode interface material electronicses transmission performance is good and property is stable, for it is organic too
The energy conversion efficiency of organic solar batteries can be improved during positive energy battery.Fourth aspect of the embodiment of the present invention aims to provide one
Kind organic solar batteries, the material of the embellishing cathode interface layer of the organic solar batteries is described in first aspect present invention
2,1,3- diazosulfide derivatives, organic solar batteries energy conversion efficiency height and stable performance.
In a first aspect, the embodiments of the invention provide a kind of 2,1,3- diazosulfide derivative, described 2,1,3- benzo
The chemical structural formula of thiadiazoles derivative such as formula（Ⅰ）It is shown：
Wherein, R1For abundant electron substituents, R2And R3In one be electron deficient substituent and another be hydrogen atom, or R2
And R3In two be electron deficient substituent.
The R1For amino, dimethylamino or lignocaine.
The R2And R3It independently is-CN ,-NO2、-COOR4、Wherein, R4
The alkyl for being 0~6 for carbon number.
The chemical structural formula of the 2,1,3- diazosulfide derivatives is one kind in the d of I a of formula~formula I：
Wherein, R4The alkyl for being 0~6 for carbon number.
First aspect of the embodiment of the present invention provides a kind of 2,1,3- diazosulfide derivative, 2,1, the 3- benzo thiophene two
Contain abundant electron substituents and electron deficient substituent in Zole derivatives simultaneously, be unsymmetric structure, cause 2,1,3- benzo thiophene two
Zole derivatives intramolecular produces electric dipole moment so that electronics has directionality in the transmission of the intramolecular, improves electric transmission
Efficiency.2,1, the 3- diazosulfide derivative is during film forming is prepared, due to the characteristic of its self assembly, electron deficient substitution
Base is easily enriched in the photoelectric active layer position of battery, and abundant electron substituents are then easily enriched in cathode material position.Electron deficient takes
Dai Ji is easy to extract electronics from the organic active layer material in photoelectric active layer, and electronics is transferred to the direction of electric dipole moment
Abundant electron substituents position, is then extracted by cathode material, is advantageous to the directional transmission of electronics, so as to improve the photoelectricity of battery
Conversion efficiency.Meanwhile in 2,1, the 3- diazosulfide derivative diazosulfide unit and electron deficient substituent formed it is big
Conjugated system, there is wider energy band and high electron affinity energy, improve 2, the electronics of 1,3- diazosulfide derivative passes
Defeated efficiency.
Described 2,1,3- diazosulfide derivative is Small molecule organic materials, and molecular weight is fixed, and property is stable, overcomes
When embellishing cathode interface material is polymeric material in the prior art, material molecule amount is inconsistent to cause organic solar batteries steady
The problem of property difference, so as to improve the stability of organic solar batteries and energy conversion efficiency.
Meanwhile 2, there is electron deficient substituent in 1,3- diazosulfide derivative, move down the band gap of the derivative, keep away
Exempt from hole and transported to negative electrode, the presence of electron deficient substituent from photoelectric active layer also improve described 2,1,3- diazosulfide
The electric conductivity of derivative.
In addition, when abundant electron substituents are dimethylamino, water/alcohol of 2,1,3- diazosulfide derivative can be improved
Dissolubility, will not be in solar cell when described 2,1,3- diazosulfide derivatives are prepared into solution spin coating film
Photoelectric activity layer material produces dissolution, is advantageous to 2,1,3- diazosulfide derivative follow-up processing and application.By 2,
When 1,3- diazosulfide derivative is used for the embellishing cathode interface layer of solar cell, be advantageous to the directional transmission of electronics,
So as to improve the efficiency of battery device.
Second aspect, the embodiments of the invention provide a kind of preparation method of 2,1,3- diazosulfide derivative, including
Following steps：
Compound of the chemical structural formula as shown in formula A and the compound as shown in formula B are provided respectively,
A：B：
Wherein, R1For abundant electron substituents, R2And R3In one be electron deficient substituent and another be hydrogen atom, or R2
And R3In two be electron deficient substituent；
It is 1 by mol ratio under oxygen-free environment:1~1:10 compound as shown in formula A and the change as shown in formula B
Compound, which is added into the organic solvent containing catalyst, to be dissolved, and obtains mixed solution, by the mixed solution at 40 DEG C~150 DEG C
Lower carry out knoevenagel condensation, reaction time are 4~48 hours, obtain product, and the organic solvent is acetonitrile, second
Acid, toluene, acetic anhydride or N,N-dimethylformamide；Then stop reacting and be cooled to room temperature, by the product silicagel column
Chromatography method purifies, and obtains structural formula such as formula（Ⅰ）The shown 2,1,3- diazosulfide derivatives：
The catalyst is piperidines, basic alumina or triethylamine.
The mole of the catalyst is the 2%~10% of the mole of the compound as shown in formula A.
Concentration of the compound in the mixed solution as shown in formula A is 20mg/ml~50mg/ml.
The R1For amino, dimethylamino or lignocaine.
The R2And R3It independently is-CN ,-NO2、-COOR4、Wherein, R4
The alkyl for being 0~6 for carbon number.
The chemical structural formula of the 2,1,3- diazosulfide derivatives is one kind in the d of I a of formula~formula I：
Wherein, R4The alkyl for being 0~6 for carbon number.
Second aspect of the embodiment of the present invention provides a kind of preparation method of 2,1,3- diazosulfide derivative, the preparation
Method is simple, and obtained 2,1,3- diazosulfide derivative electronic transmission performance is good and property is stable.
The third aspect, the embodiments of the invention provide a kind of embellishing cathode interface material, the embellishing cathode interface material
Chemical structural formula such as formula（Ⅰ）It is shown：
Wherein, R1For abundant electron substituents, R2And R3In one be electron deficient substituent and another be hydrogen atom, or R2
And R3In two be electron deficient substituent.
The R1For amino, dimethylamino or lignocaine.
The R2And R3It independently is-CN ,-NO2、-COOR4、Wherein, R4
The alkyl for being 0~6 for carbon number.
The chemical structural formula of the 2,1,3- diazosulfide derivatives is one kind in the d of I a of formula~formula I：
Wherein, R4The alkyl for being 0~6 for carbon number.
The inventive embodiments third aspect provides a kind of embellishing cathode interface material, and the embellishing cathode interface material electronicses pass
Defeated functional and property is stable, and the energy conversion effect of organic solar batteries can be improved during for organic solar batteries
Rate.
Fourth aspect, the embodiments of the invention provide a kind of organic solar batteries, the solar cell for it is formal too
It is positive can battery or trans solar cell, transparent substrates that the formal solar cell includes stacking gradually, anode layer, anode
Decorative layer, photoelectric active layer, embellishing cathode interface layer and cathode layer, the trans solar cell are transparent including stacking gradually
Substrate, cathode layer, embellishing cathode interface layer, photoelectric active layer, anode modification layer and anode layer, the embellishing cathode interface layer
The chemical structural formula of material such as formula（Ⅰ）It is shown：
Wherein, R1For abundant electron substituents, R2And R3In one be electron deficient substituent and another be hydrogen atom, or R2
And R3In two be electron deficient substituent.
The R1For amino, dimethylamino or lignocaine.
The R2And R3It independently is-CN ,-NO2、-COOR4、Wherein, R4
The alkyl for being 0~6 for carbon number.
The chemical structural formula of the 2,1,3- diazosulfide derivatives is one kind in the d of I a of formula~formula I：
Wherein, R4The alkyl for being 0~6 for carbon number.
The thickness of the embellishing cathode interface layer is 5nm~20nm.
The transparent substrates select glass or polyester film.
The material of the anode layer is tin indium oxide（ITO）, aluminium, silver or gold.
The anode modification layer is the composite membrane or molybdenum oxide film of Polyglycolic acid fibre and kayexalate.
Contain electron donor unit and electron acceptor list in the chemical formula of electron donor material in the photoelectric active layer
Member, or contain one or more of electron donor units.
The electron donor material is coughs up or the polymerization of fluorenes containing thiophene, Dithiophene acene, thienothiophene, dithieno thiophene
Thing or small molecule.The electron acceptor material is fullerene and its derivative.
The middle electron donor of the photoelectric active layer is poly- 3 hexyl thiophene（P3HT), the electron acceptor is [6,6]-benzene
Base C71 methyl butyrates（PCBM, [6,6]-phenyl-C61-butyric acid methyl ester).
The cathode layer material is aluminium, silver, copper or ITO.
Fourth aspect of the embodiment of the present invention provides a kind of organic solar batteries, negative electrode circle of the organic solar batteries
The material of face decorative layer be first aspect present invention described in the diazosulfide derivative of one kind 2,1,3-, the organic solar
Cell power conversion efficiency is high and property is stable.
A kind of preparation method of formal organic solar batteries, comprises the following steps：
(1) anode layer, anode modification layer and photoelectric active layer are sequentially prepared on a transparent substrate；
(2) by chemical structural formula chemical structural formula such as formula（Ⅰ）Shown 2,1,3- diazosulfide derivatives are dissolved in molten
In agent, the mixed liquor that 2,1,3- diazosulfide derivative concentration is 10mg/ml~15mg/ml is obtained, in the photoelectric activity
Mixed liquor described in spin coating in layer surface, spin speed are 500rpm~2000rpm, and spin-coating time is 1~5 minute, and spin coating terminates
Afterwards, 20 minutes~1 hour is stood, obtains embellishing cathode interface layer, the solvent is isopropanol, isooctanol, ethanol, acetic acid, second
Acetoacetic ester, petroleum ether, methanol or water；
Wherein, R1For abundant electron substituents, R2 and R3 independently are hydrogen atom or electron deficient substituent, R2And R3At least
One is electron deficient substituent；
(3) cathode layer is prepared on the embellishing cathode interface layer, obtains the organic solar batteries.
The R1 is amino, dimethylamino or lignocaine.
The R2And R3It independently is-CN ,-NO2、-COOR4、Wherein, R4
The alkyl for being 0~6 for carbon number.
The chemical structural formula of the 2,1,3- diazosulfide derivatives is one kind in the d of I a of formula~formula I：
Wherein, R4The alkyl for being 0~6 for carbon number.
A kind of preparation method of trans organic solar batteries, comprises the following steps：
(1) cathode layer is prepared on a transparent substrate；
(2) by chemical structural formula chemical structural formula such as formula（Ⅰ）Shown 2,1,3- diazosulfide derivatives are dissolved in molten
In agent, the mixed liquor that 2,1,3- diazosulfide derivative concentration is 10mg/ml~15mg/ml is obtained, in the cathode layer table
Mixed liquor described in spin coating on face, spin speed are 500rpm~2000rpm, and spin-coating time is 1~5 minute, quiet after spin coating terminates
Put 20 minutes~1 hour, obtain embellishing cathode interface layer, the solvent is isopropanol, isooctanol, ethanol, acetic acid, acetic acid second
Ester, petroleum ether, methanol or water；
Wherein, R1For abundant electron substituents, R2And R3It independently is hydrogen atom or electron deficient substituent, R2And R3At least one
Individual is electron deficient substituent；
(3) photoelectric active layer, anode modification layer and anode layer are sequentially prepared on the embellishing cathode interface layer, obtain institute
State organic solar batteries.
Step（2）It is middle by chemical structural formula chemical structural formula such as formula（Ⅰ）Shown embellishing cathode interface material is dissolved in
After solvent, stirring 6h~10h in agitator is placed in, obtains the mixed liquor.
The thickness of the embellishing cathode interface layer is 5nm~20nm.
The solvent can dissolve embellishing cathode interface material, and not molten with the material generation in photoelectric active layer and negative electrode
The effect such as solution.
The solvent is isopropanol, ethanol, acetic acid or methanol.
The transparent substrates select glass or polyester film.
The material of the anode layer is tin indium oxide（ITO）, aluminium, silver or gold.
The anode modification layer is the composite membrane or molybdenum oxide film of Polyglycolic acid fibre and kayexalate.
Contain electron donor unit and electron acceptor list in the chemical formula of electron donor material in the photoelectric active layer
Member, or contain one or more of electron donor units.
The electron donor material is coughs up or the polymerization of fluorenes containing thiophene, Dithiophene acene, thienothiophene, dithieno thiophene
Thing or small molecule.The electron acceptor material is fullerene and its derivative.
The middle electron donor of the photoelectric active layer is poly- 3 hexyl thiophene（P3HT), the electron acceptor is [6,6]-benzene
Base C71 methyl butyrates（PCBM, [6,6]-phenyl-C61-butyric acid methyl ester).
The cathode layer material is aluminium, silver, copper or ITO.
The present invention prepares embellishing cathode interface layer, the thickness of embellishing cathode interface layer and the uniformity of distribution with spin coating method
It is easily controlled, preparation method will not destroy photoelectric active layer, and the stable performance for the organic solar batteries being prepared, electronics
Transporting is good, and method is simple, and cost is cheap.
The advantages of embodiment of the present invention, will partly illustrate in the following description, a part according to specification be it is aobvious and
It is clear to, or can be known by the implementation of the embodiment of the present invention.
Embodiment one
The preparation method of one kind 2,1,3- diazosulfide derivatives, comprises the following steps：
By 4- aldehyde radical -7- dimethylamino benzo thiadiazoles of the chemical structural formula as shown in formula A1 and chemical structural formula such as formula a1
Shown cyanoacetic acid base propyl diester equimolar obtains mixed solution, 4- aldehyde radicals -7- than being dissolved in the acetonitrile containing catalyst piperidines
Concentration of the dimethylamino benzo thiadiazoles in mixed solution is 20mg/ml, and the mole of piperidines is 4- aldehyde radical -7- dimethylaminos
The 2% of diazosulfide mole；Under nitrogen guard mode, solution is stirred at 80 DEG C, 4- aldehyde radicals -7- in mixed solution
Dimethylamino benzo thiadiazoles and cyanoacetic acid base Arrcostab occur knoevenagel condensation and obtain product, reaction time 4
Hour.Product is obtained into 2 shown in I a1,1,3- diazosulfide derivative, reactional equation with the Methods For Purification of silica gel column chromatography
Formula is as follows：
A kind of preparation method of formal organic solar batteries, comprises the following steps：
（1）Use liquid detergent, deionized water, acetone, isopropanol ultrasonic clear successively the transparent conducting glass that sputtering has ITO
Wash, then handle glass surface, spin coating Polyglycolic acid fibre and kayexalate on transparent conducting glass with ozone
Mixed solution as anode modification layer, then by poly- 3 hexyl thiophene（P3HT) it is spun on anode with PCBM mixed solution and repaiies
Adorn on layer, obtain photoelectric active layer；
（2）By 2 shown in I a1,1,3- diazosulfide derivative is dissolved in methanol, is stirred 6 hours on agitator,
Obtain 2,1,3- diazosulfide derivative concentration be 15mg/ml mixed liquor, the spin coating mixed liquor in photoelectric activity layer surface,
Spin speed is 1000rpm, and spin-coating time is 2 minutes, after spin coating terminates, stands 20 minutes, obtains the negative electrode that thickness is 20nm
Interface-modifying layer；
（3）Formal organic sun is obtained as negative electrode using the method AM aluminum metallization of vacuum evaporation in embellishing cathode interface layer
Can battery.
Embodiment two
The preparation method of one kind 2,1,3- diazosulfide derivatives, comprises the following steps：
By 4- aldehyde radical -7- dimethylamino benzo thiadiazoles of the chemical structural formula as shown in formula A1 and chemical structural formula such as formula a2
Shown cyanoacetic acid base hexyl ester is 1 in molar ratio:10 are dissolved in the toluene containing catalyst basic alumina, are mixed
Solution is closed, concentration of the 4- aldehyde radical -7- dimethylamino benzo thiadiazoles in mixed solution is 50mg/ml, basic alumina
Mole be 4- aldehyde radical -7- dimethylamino benzo thiadiazoles moles 10%；Under nitrogen guard mode, stirred at 40 DEG C
Mixed solution, Borneo camphor Wen Gaier occurs for 4- aldehyde radical -7- dimethylamino benzo thiadiazoles and cyanoacetic acid base Arrcostab in mixed solution
Condensation reaction obtains product, and the reaction time is 24 hours.Product is obtained into 2 shown in I a2 with the Methods For Purification of silica gel column chromatography,
1,3- diazosulfide derivative, reaction equation are as follows：
A kind of preparation method of formal organic solar batteries, comprises the following steps：
（1）Use liquid detergent, deionized water, acetone, isopropanol ultrasonic clear successively the transparent conducting glass that sputtering has ITO
Wash, then handle glass surface, spin coating Polyglycolic acid fibre and kayexalate on transparent conducting glass with ozone
Mixed solution as anode modification layer, then by poly- 3 hexyl thiophene（P3HT) it is spun on anode with PCBM mixed solution and repaiies
Adorn on layer, obtain photoelectric active layer；
（2）By 2 shown in I a2,1,3- diazosulfide derivative is dissolved in methanol, is stirred 6 hours on agitator,
Obtain 2,1,3- diazosulfide derivative concentration be 15mg/ml mixed liquor, the spin coating mixed liquor in photoelectric activity layer surface,
Spin speed is 500rpm, and spin-coating time is 5 minutes, after spin coating terminates, stands 20 minutes, obtains negative electrode circle that thickness is 20nm
Face decorative layer；
（3）Organic solar electricity is obtained as negative electrode using the method AM aluminum metallization of vacuum evaporation in embellishing cathode interface layer
Pond.
Embodiment three
The preparation method of one kind 2,1,3- diazosulfide derivatives, comprises the following steps：
By 4- aldehyde radical -7- dimethylamino benzo thiadiazoles of the chemical structural formula as shown in formula A1 and chemical structural formula such as formula a3
Shown cyanoacetic acid is 1 in molar ratio:5 are dissolved in the acetic acid containing catalyst of triethylamine, obtain mixed solution, 4- aldehyde radicals -7-
Concentration of the dimethylamino benzo thiadiazoles in mixed solution is 40mg/ml, and the mole of triethylamine is 4- aldehyde radical -7- diformazan ammonia
The 5% of base diazosulfide mole；Under nitrogen guard mode, solution is stirred at 100 DEG C, 4- aldehyde radicals in mixed solution-
7- dimethylamino benzo thiadiazoles and cyanoacetic acid occur knoevenagel condensation and obtain product, and the reaction time is 24 hours.
Product is obtained into 2 shown in I a3 with the Methods For Purification of silica gel column chromatography, 1,3- diazosulfide derivative, reaction equation is such as
Under：
A kind of preparation method of formal organic solar batteries, comprises the following steps：
（1）Use liquid detergent, deionized water, acetone, isopropanol ultrasonic clear successively the transparent conducting glass that sputtering has ITO
Wash, then handle glass surface, spin coating Polyglycolic acid fibre and kayexalate on transparent conducting glass with ozone
Mixed solution as anode modification layer, then by poly- 3 hexyl thiophene（P3HT) it is spun on anode with PCBM mixed solution and repaiies
Adorn on layer, obtain photoelectric active layer；
（2）By 2 shown in I a3,1,3- diazosulfide derivative is dissolved in methanol, is stirred 6 hours on agitator,
Obtain 2,1,3- diazosulfide derivative concentration be 15mg/ml mixed liquor, the spin coating mixed liquor in photoelectric activity layer surface,
Spin speed is 1000rpm, and spin-coating time is 2 minutes, after spin coating terminates, stands 20 minutes, obtains the negative electrode that thickness is 20nm
Interface-modifying layer；
（3）Organic solar electricity is obtained as negative electrode using the method AM aluminum metallization of vacuum evaporation in embellishing cathode interface layer
Pond.
Example IV
The preparation method of one kind 2,1,3- diazosulfide derivatives, comprises the following steps：
By 4- aldehyde radical -7- dimethylamino benzo thiadiazoles of the chemical structural formula as shown in formula A1 and chemical structural formula such as formula b
Shown malononitrile equimolar obtains mixed solution, 4- aldehyde radical -7- diformazans than being dissolved in the acetic anhydride containing catalyst piperidines
Concentration of the amino diazosulfide in mixed solution is 40mg/ml, and the mole of piperidines is 4- aldehyde radical -7- dimethylamino benzos
The 4% of thiadiazoles mole；Under nitrogen guard mode, solution is stirred at 50 DEG C, 4- aldehyde radical -7- diformazan ammonia in mixed solution
Base diazosulfide and malononitrile occur knoevenagel condensation and obtain product, and the reaction time is 10 hours.Product is used
The Methods For Purification of silica gel column chromatography obtains 2 shown in I b, 1,3- diazosulfide derivative, and reaction equation is as follows：
A kind of preparation method of trans organic solar batteries, comprises the following steps：
（1）Use liquid detergent, deionized water, acetone, isopropanol ultrasonic clear successively the transparent conducting glass that evaporation has aluminium
Wash, then handle glass surface with ozone；
（2）By 2 shown in I b, 1,3- diazosulfide derivative is dissolved in methanol, is stirred 10 hours on agitator,
The mixed liquor that 2,1,3- diazosulfide derivative concentration is 15mg/ml is obtained, the spin coating mixing on transparent conductive glass surface
Liquid, spin speed 1000rpm, spin-coating time is 2 minutes, after spin coating terminates, stands 20 minutes, obtains the moon that thickness is 20nm
Pole interface-modifying layer；
（3）P3HT and PCBM mixed solution is spun on embellishing cathode interface layer, obtains photoelectric active layer；Then will
The mixed solution spin coating of Polyglycolic acid fibre and kayexalate is made in obtain anode modification layer on photoelectric active layer,
Anodic interface decorative layer, as anode, obtains organic solar batteries using the method AM aluminum metallization of vacuum evaporation.
Embodiment five
The preparation method of one kind 2,1,3- diazosulfide derivatives, comprises the following steps：
By 4- aldehyde radical -7- dimethylamino benzo thiadiazoles of the chemical structural formula as shown in formula A1 and chemical structural formula such as formula c
Shown 2,6- dimethyl -4- pyrans subunit malononitrile equimolar is than being dissolved in the N containing catalyst piperidines, N- dimethyl formyls
In amine, mixed solution is obtained, concentration of the 4- aldehyde radical -7- dimethylamino benzo thiadiazoles in mixed solution is 40mg/ml, piperidines
Mole be 4- aldehyde radical -7- dimethylamino benzo thiadiazoles moles 6%；Under nitrogen guard mode, stirred at 100 DEG C
Mixed solution, 4- aldehyde radical -7- dimethylamino benzo thiadiazoles and 2,6- dimethyl -4- pyrans subunits malononitrile hair in mixed solution
Raw knoevenagel condensation obtains product, and the reaction time is 10 hours.Product is obtained with the Methods For Purification of silica gel column chromatography
It is as follows to the embellishing cathode interface material shown in I c, reaction equation：
A kind of preparation method of formal organic solar batteries, comprises the following steps：
（1）Use liquid detergent, deionized water, acetone, isopropanol ultrasonic clear successively the transparent conducting glass that sputtering has ITO
Wash, then handle glass surface, spin coating Polyglycolic acid fibre and kayexalate on transparent conducting glass with ozone
Mixed solution as anode modification layer, then P3HT and PCBM mixed solution are spun in anode modification layer, obtain light
Electroactive layer；
（2）By 2 shown in I c, 1,3- diazosulfide derivative is dissolved in acetic acid, is stirred 8 hours on agitator,
Obtain 2,1,3- diazosulfide derivative concentration be 10mg/ml mixed liquor, the spin coating mixed liquor in photoelectric activity layer surface,
Spin speed is 1000rpm, and spin-coating time is 3 minutes, after spin coating terminates, stands 1 hour, obtains negative electrode circle that thickness is 15nm
Face decorative layer；
（3）Organic solar electricity is obtained as negative electrode using the method AM aluminum metallization of vacuum evaporation in embellishing cathode interface layer
Pond.
Embodiment six
The preparation method of one kind 2,1,3- diazosulfide derivatives, comprises the following steps：
By 4- aldehyde radical -7- dimethylamino benzo thiadiazoles of the chemical structural formula as shown in formula A1 and chemical structural formula such as formula d
Shown 2- (3,5,5- trimethyl-cyclohexane -2- alkenyl -1- subunits) malononitrile equimolar ratio is dissolved in containing catalyst piperidines
Acetonitrile in, obtain mixed solution, concentration of the 4- aldehyde radical -7- dimethylamino benzo thiadiazoles in mixed solution is 40mg/ml,
The mole of piperidines is the 5% of 4- aldehyde radical -7- dimethylamino benzo thiadiazoles moles；Under nitrogen guard mode, stirred at 80 DEG C
Mix mixed solution, 4- aldehyde radical -7- dimethylamino benzo thiadiazoles and 2- (3,5,5- trimethyl-cyclohexane -2- alkene in mixed solution
Base -1- subunits) malononitrile occurs knoevenagel condensation and obtains product, and the reaction time is 15 hours.By product silica gel
The Methods For Purification of column chromatography obtains 2 shown in I d, 1,3- diazosulfide derivative, and reaction equation is as follows：
A kind of preparation method of formal organic solar batteries, comprises the following steps：
（1）Use liquid detergent, deionized water, acetone, isopropanol ultrasonic clear successively the transparent conducting glass that sputtering has ITO
Wash, then handle glass surface, spin coating Polyglycolic acid fibre and kayexalate on transparent conducting glass with ozone
Mixed solution as anode modification layer, then P3HT and PCBM mixed solution are spun in anode modification layer, obtain light
Electroactive layer；
（2）By 2 shown in I d, 1,3- diazosulfide derivative is dissolved in acetic acid, is stirred 10 hours on agitator,
Obtain 2,1,3- diazosulfide derivative concentration be 10mg/ml mixed liquor, the spin coating mixed liquor in photoelectric activity layer surface,
Spin speed is 2000rpm, and spin-coating time is 1 minute, after spin coating terminates, stands 1 hour, obtains negative electrode circle that thickness is 5nm
Face decorative layer；
（3）Organic solar electricity is obtained as negative electrode using the method AM aluminum metallization of vacuum evaporation in embellishing cathode interface layer
Pond.
Comparative example
A kind of preparation method of formal organic solar batteries, comprises the following steps：
（1）Use liquid detergent, deionized water, acetone, isopropanol ultrasound clear successively the transparent conducting glass that sputtering has ITO
Wash, then handle glass surface, spin coating Polyglycolic acid fibre and kayexalate on transparent conducting glass with ozone
Mixed solution as anode modification layer, then by poly- 3 hexyl thiophene（P3HT) it is spun on anode with PCBM mixed solution and repaiies
Adorn on layer, obtain photoelectric active layer；
（2）Organic solar batteries are obtained as negative electrode using the method AM aluminum metallization of vacuum evaporation on photoelectric active layer.
The organic solar that the organic solar batteries and comparative example that the present embodiment 1~6 is prepared are prepared
Battery is compared, and the organic solar batteries energy conversion efficiency that the present embodiment 1~6 is prepared improves 10%~20%.This says
Bright, 2,1, the 3- diazosulfide derivative electronic transmission performance that first aspect of the embodiment of the present invention provides is good and property is steady
Fixed, 2,1, the 3- diazosulfide derivative is used to that during organic solar batteries embellishing cathode interface layer organic sun can be improved
The energy conversion efficiency of energy battery.
Claims (8)
1. one kind 2,1,3- diazosulfide derivatives, it is characterised in that shown in chemical structural formula such as formula (I)：
Wherein, R1For dimethylamino or lignocaine, R2And R3In one be electron deficient substituent and another be hydrogen atom, or R2
And R3In two be electron deficient substituent, the electron deficient substituent is-CN ,-NO2、-COOR4、Wherein, R4The alkyl for being 0~6 for carbon number.
2. 2,1,3- diazosulfide derivative of one kind as claimed in claim 1, it is characterised in that described 2,1,3- benzo thiophene
The chemical structural formula of oxadiazole derivative is one kind in the d of I a of formula~formula I：
Wherein, R4The alkyl for being 0~6 for carbon number.
3. one kind 2,1, the preparation method of 3- diazosulfide derivatives, it is characterised in that comprise the following steps：
Compound of the chemical structural formula as shown in formula A and the compound as shown in formula B are provided respectively,
A：B：
Wherein, R1For dimethylamino or lignocaine, R2And R3In one be electron deficient substituent and another be hydrogen atom, or R2And R3In
Two are electron deficient substituent；The electron deficient substituent is-CN ,-NO2、-COOR4、
Wherein, R4The alkyl for being 0~6 for carbon number；
It is 1 by mol ratio under oxygen-free environment:1~1:10 compound as shown in formula A and the compound as shown in formula B add
Add in the organic solvent containing catalyst and dissolve, obtain mixed solution, the mixed solution is carried out at 40 DEG C~150 DEG C
Knoevenagel condensation, reaction time are 4~48 hours, obtain product, the organic solvent be acetonitrile, acetic acid, toluene,
Acetic anhydride or N,N-dimethylformamide；Then stop reacting and be cooled to room temperature, by the product silica gel column chromatography method
Purification, obtains described 2 of structural formula as shown in formula (I), 1,3- diazosulfide derivative；
Wherein, R1For dimethylamino or lignocaine, R2And R3In one be electron deficient substituent and another be hydrogen atom, or R2
And R3In two be electron deficient substituent, the electron deficient substituent is-CN ,-NO2、-COOR4、Wherein, R4The alkyl for being 0~6 for carbon number.
4. as claimed in claim 32, the preparation method of 1,3- diazosulfide derivative, it is characterised in that the catalyst
For piperidines, basic alumina or triethylamine.
5. as claimed in claim 32, the preparation method of 1,3- diazosulfide derivative, it is characterised in that described 2,1,3-
The chemical structural formula of diazosulfide derivative is one kind in the d of I a of formula~formula I：
Wherein, R4The alkyl for being 0~6 for carbon number.
A kind of 6. embellishing cathode interface material, it is characterised in that the chemical structural formula such as formula (I) of the embellishing cathode interface material
It is shown：
Wherein, R1For dimethylamino or lignocaine, R2And R3In one be electron deficient substituent and another be hydrogen atom, or R2
And R3In two be electron deficient substituent, the electron deficient substituent is-CN ,-NO2、-COOR4、Wherein, R4The alkyl for being 0~6 for carbon number.
7. a kind of organic solar batteries, the solar cell is formal solar cell or trans solar cell, described
Transparent substrates that formal solar cell includes stacking gradually, anode layer, anode modification layer, photoelectric active layer, cathode interface are repaiied
Adorn layer and cathode layer, transparent substrates that the trans solar cell includes stacking gradually, cathode layer, embellishing cathode interface layer,
Photoelectric active layer, anodic interface decorative layer and anode layer, it is characterised in that the chemistry knot of the material of the embellishing cathode interface layer
Shown in structure formula such as formula (I)：
Wherein, R1For dimethylamino or lignocaine, R2And R3In one be electron deficient substituent and another be hydrogen atom, or R2
And R3In two be electron deficient substituent, the electron deficient substituent is-CN ,-NO2、-COOR4、Wherein, R4The alkyl for being 0~6 for carbon number.
A kind of 8. organic solar batteries as claimed in claim 7, it is characterised in that the material of the embellishing cathode interface layer
Chemical structural formula be the d of I a of formula~formula I in one kind：
Wherein, R4The alkyl for being 0~6 for carbon number.
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